Selenoimidoylation of Alcohols with Selenium and Isocyanides and Its Application to the Synthesis of Selenium-Containing Heterocycles

The reaction of alcohols with selenium and
isocyanides in the presence of DBU gave oxyimidoylselenoates 6. Trapping of 6 with BuI resulted in high-yield
formation of selenocarbonimidates 4. When alk-2-yn-1-ols
9 were allowed to react with selenium and isocyanides under
similar conditions, new selenium-containing heterocycles 10,
2-imino-4-alkylidene-1,3-oxaselenolanes, were obtained via
cycloaddition of oxyimidoylselenoates 13 generated in situ
by intramolecular addition of selenolates to carbon−carbon
triple bonds.

在1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）存在下，醇与硒单质及异氰化物发生反应，得到氧亚胺酰硒代酸酯类化合物6。采用碘丁烷（BuI）对化合物6进行捕获，可高产率生成硒代碳亚胺酯类化合物4。在相似条件下，使2-炔-1-醇类化合物9与硒单质及异氰化物反应，通过硒醇负离子对碳碳三键的分子内加成原位生成的氧亚胺酰硒代酸酯13发生环加成反应，即可得到新型含硒杂环化合物10——2-亚氨基-4-亚烷基-1,3-氧硒戊环。